DE102006009196A1 - Luminescence signal referencing standard, has base material including volume doping with constituent part that is fluorescent and luminescent and includes rare earth metal and/or non-ferrous material e.g. cobalt, chrome or manganese - Google Patents

Abstract

The standard has a transparent base material that is made of a lanthanum-phosphate-glass, a fluorine-phosphate glass, a fluorine-crown glass, a lanthanum glass, a glass ceramic or a lithium-aluminosilicate-glass ceramic. The base material has a volume doping with a constituent part that is fluorescent and luminescent. The constituent part has a rare earth metal and/or a non-ferrous material e.g. cobalt, chrome or manganese. Independent claims are also included for the following: (1) a method for producing a standard (2) an application of the standard as a luminescence standard for characterizing a long-time stability of a luminescence measuring system.

Description

The This invention relates to a standard for referencing luminescent signals, and a method for producing such a standard and advantageous uses of such a standard.

The Results of luminescence measurements include the desired ones Measurement data of the analysis also device-dependent contributions, the a comparability of Lumineszenzmessdaten on equipment and laboratory limits and make long-term comparability very difficult or almost impossible. For the Comparability of Lumineszenzmessdaten in the spectral range, the ranging from UV to NIR (near infrared) is a standardization the spectral parameters and the sensitivity parameter of luminescence measuring systems necessary. About that have to go out typically the wavelength accuracy and the linearity the detection systems are checked. To the solution This problem is defined reference systems such as Luminescence standards required. Standardization of the spectral Characteristics of luminescence measuring systems can be independent of the standardization of the sensitivity parameters, either Lumineszenzintensitätsstandards or absolute measurements of the luminescence intensity or the luminescence quantum yield requires. Alternative to physical transfer standards such as Example of receiver standards for determining the wavelength dependence the spectral illuminance of the Excitation channels of standard lamps or radiance standards for Determination of the wavelength dependence the spectral sensitivity of the emission channel, can spectral characterization of luminescence measuring systems also chemical Transfer standards or so-called Lumineszenzstandards used become.

• – je nach Zusammensetzung Lumineszenz im UV- bis NIR-Spektralbereich,
• – für spektrale Standards möglichst breite, unstrukturierte Lumineszenzspektren,
• – eine hohe und bekannte Reinheit,
• – eine möglichst geringe Überlappung zwischen Absorptions- und Emissionsspektren,
• – eine wellenlängenunabhängige Quantenausbeute der Lumineszenz (im für die Gerätecharakterisierung verwendeten Spektralbereich),
• – eine isotrope Emission,
• – eine geringe Variation der Intensität an einer statistisch relevanten Anzahl von Messpunkten, d.h. eine hohe Homogenität,
• – eine möglichst geringe und/oder bekannte Temperaturabhängigkeit der Lumineszenz im relevanten Bereich der Umgebungstemperatur,
• – Lumineszenzlebensdauern im Bereich von Nanosekunden, Mikrosekunden oder Millisekunden (für Lebensdauerstandards),
• – möglichst viele schmale Banden im UV- bis NIR-Spektralbereich (für Wellenlängenstandards, Day-To-Day-Performance, Langzeitstabilität, Intensitätsstandards),
• – eine bekannte und hinreichende Langzeitstabilität (thermisch und photochemisch),
• – eine hohe Reproduzierbarkeit bei „Single Use-Standards",
• – eine Möglichkeit zur Messung von Probe- und Transferstan dard unter identischen Messbedingungen (zum Beispiel auch identische Messparameter und Messgeometrie, Probenformate, wie Küvette, Slide, Mikrotiterplatte), bei vergleichbaren Signalintensitäten/Photonenzählraten, mit möglichst ähnlichen Emissionscharakteristika.

In addition to spectral standards and intensity standards, standards that are easy to handle and stable over the long term are required for the characterization and verification of the wavelength accuracy, for the characterization of the day-to-day performance and for the acquisition of device aging (spectral effects and sensitivity). Among the requirements that standards for the referencing of luminescent signals (hereinafter "luminescence standards") are made, among others, depending on the particular field of application

• - Depending on the composition, luminescence in the UV to NIR spectral range,
• For spectral standards as broad, unstructured luminescence spectra as possible,
• A high and known purity,
• A minimum overlap between absorption and emission spectra,
• A wavelength-independent quantum efficiency of the luminescence (in the spectral range used for device characterization),
• An isotropic emission,
• A small variation of the intensity at a statistically relevant number of measuring points, ie a high homogeneity,
• A lowest possible and / or known temperature dependence of the luminescence in the relevant region of the ambient temperature,
• Luminescence lifetimes in the range of nanoseconds, microseconds or milliseconds (for lifetime standards),
• - as many narrow bands as possible in the UV to NIR spectral range (for wavelength standards, day-to-day performance, long-term stability, intensity standards),
• A known and sufficient long-term stability (thermal and photochemical),
• - high reproducibility in "single use standards",
• A possibility for the measurement of sample and transfer standards under identical measurement conditions (for example also identical measurement parameters and measurement geometry, sample formats, such as cuvette, slide, microtiter plate), at comparable signal intensities / photon counting rates, with as similar emission characteristics as possible.

Around Luminescence properties, which are generally arbitrary and relative units can be measured to make comparable Luminescence standards have become known in the prior art, However, in many cases not sufficient long-term stability, homogeneity or isotropy or toxic or environmentally harmful materials, such as Contain cadmium or uranium.

For example, US-A-4302678 discloses a standard for calibrating a UV scanning system used to detect surface defects on workpieces. The standard consists of a yellow potassium borosilicate glass containing uranium oxide. The use of uranium oxide is because of the associated necessary safety measures and environmental issues considered disadvantageous. In addition, such a standard does not have the necessary photostability and long-term stability.

Out WO-A-0106227 are standards for the referencing of fluorescence signals known, the sol gel glasses, other glasses or polymers in which received luminescent micro or nanoparticles are. These are in particular luminescent nanoparticles from polymers and metal-ligand complexes of ruthenium, osmium, Rhenium, iridium, platinum or palladium.

From EP-B-0926102 a luminescent glass with long persistence time is known, which can be used as a night light, night signal, material for confirming an infrared laser or the like. It is an oxide glass which, when excited by radiation such as gamma rays, X-rays or UV rays, may exhibit long-lasting persistence and photostimulated luminescence, the glass containing 1 to 55 wt% SiO ₂ , 1 to 50 wt% B ₂ O ₃ , 30 to 75 wt .-% ZnO, further optional ingredients and terbium or manganese as a fluorescer.

One however, such glass is not usable as a luminescent standard.

As filter glasses, a number of colored glasses are known, which can be used as a steep edge filter. These include DE-B-10141104, from which a colored optical glass for a steep edge filter is known, the 30 to 75 wt .-% SiO ₂ , 5 to 35 wt .-% K ₂ O, 0 to 5 wt .-% TiO ₂ , 4 to 7 wt .-% B ₂ O ₃ , 5 to 30 wt .-% ZnO, 0.01 to 10 wt .-% F, and 0.1 to 3 wt .-%, copper, silver, indium , Gallium, aluminum, yttrium, sulfur, selenium or tellurium. This is a color start-up glass in which the color is produced by colloidal precipitation of semiconductor compounds during cooling of the melt or by subsequent heat treatment.

Further Color glasses more similar Species are known from DE-B-10141101 and from DE-A-2621741.

Out US-A-3773530 discloses another colored glass for a filter which Cadmium sulfide as a coloring Component contains.

such colored glasses do not have sufficiently high photostability to be luminescent standards to be used.

luminescence with fluorescent polymer layers on a non-fluorescent carrier are known from WO-A-02077620.

Out WO-A-0159503 is a luminescent standard with a substrate made of quartz, on which a textured surface is made fluorescent material is applied.

From the DE 202004002064 U1 For example, a microray support is known which contains a substantially non-fluorescent substrate as a support and at least one standard for fluorescence measurements comprising a colored glass. The colored glass contains semiconductor compounds which may be cadmium semiconductor compounds or copper, silver, indium, gallium, aluminum, sulfur or selenium semiconductor compounds. The colored glasses contain 30 to 75 wt .-% SiO ₂ , 5 to 35 wt .-% K ₂ O, 0 to 5 wt .-% TiO ₂ , 0.01 to 10 wt .-% fluorine and 0.1 to 3 Wt% of M'M '''Y'' ₂ , where M' is Cu ⁺ and / or Ag ⁺ , M '''is In ³⁺ and / or Ga ³⁺ and / or Al ³⁺ and Y is '' S is ^2- and / or Se ^2- . The fluorescent semiconductor compounds are formed as colloidal nanocrystals distributed in glass.

Furthermore However, there is a need at higher value Standards that are characterized by a particularly high quality, ie in particular have a high homogeneity and isotropy, a low temperature dependence and long-term stability and photostability. With such standards could even more stringent requirements are met, such as a review of spectral sensitivity and wavelength accuracy. Also could the Timeline in time-resolved Luminescence measurements tested become.

The Color glasses known in the art are known to be such Requirements do not do it justice, as they are not photostable. Also the remaining Luminescent standards known in the art have none sufficient quality on.

Of the Invention is therefore the object of a standard for referencing of luminescence signals (luminescence standard), which the Disadvantages of the prior art avoids as possible and a preferably high quality having. Furthermore, a manufacturing method and an advantageous Use of such a standard can be specified.

These The task is solved by a standard for the referencing of luminescence signals solved, with an optically transparent base material of a lanthanum-phosphate glass, a fluorine-phosphate glass, a Fluorite crown glass, a lanthanum glass, a glass ceramic formed from it or from a lithium aluminosilicate glass-ceramic, wherein the base material is a volume doping with a rare earth metal and / or a non-ferrous metal, in particular cobalt, chromium or manganese, contains which is fluorescent or luminescent.

The The object of the invention is completely solved in this way.

One Inventive standard is characterized by a particularly good homogeneity, isotropy, long-term stability and photostability.

Of the Inventive standard Because of its high quality for a wide variety of applications be used. For example, it can be used as a luminescence standard for characterization the long-term stability be used by Lumineszenzmesssystemen. Furthermore, a Use as wavelength standard, as luminescence intensity and luminescence lifetime standard for the spectral range from UV to NIR and for comparability and standardization of luminescence measurement data allows. This can be statements to change the spectral sensitivity of the detection system and the wavelength accuracy, for determination and characterization of the wavelength accuracy, for calibration of luminescence intensities and for the characterization and calibration of luminescence measuring systems with time-resolved Luminescence detection in the UV to NIR spectral range are taken. The standard of the invention is also suitable as a reference system or standard for characterization the (intrinsic) luminescence of materials in the UV to NIR spectral range of 250 to 1700 nm.

The Lifetime and cooldowns can be set by specifying the base material, by the concentration of the doping and by redox processes "adjust".

The Absorption and emission cross sections can be extended in a wide range Borders vary, especially if the base material is a glass ceramic is used.

In contrast to prior-art colored glasses, the crystallites in the inventive glass-ceramic (eg, doped Robax ^®)> 10 nm are. The fluorescent dopant is not incorporated in the inventive colloidal standard as in known in the art standards.

If doping with non-ferrous metals is used, then broad, unstructured emission bands result and the standards can be applied up to the NIR range (for example, with dopants with Cr ³⁺ ). No spectral fluorescence standard for the NIR range has hitherto been known in the prior art.

Become Dopings used with rare earths, resulting in sharp Line spectra, for example, for wavelength calibration or to verify the Wavelength accuracy and for determining the spectral resolution of luminescence measuring systems can be used.

The Inventive Lumineszenzstandards can for different Measuring geometries and formats are produced, so for example in cuvette form, in slide form as microplates and the like more.

By a variation of the doping concentration, the fluorescence intensity in appropriate Be influenced.

According to a further embodiment of the invention, the base material is a lanthanum-phosphate glass containing 30 to 90 wt .-% P ₂ O ₅ , preferably 50 to 80 wt .-%, particularly preferably 60 to 75 wt .-% P ₂ O. ₅ , and contains refining agent in conventional amounts.

Furthermore, the lanthanum-phosphate glass, 1 to 30 wt .-% La ₂ O ₃ , preferably 5 to 20 wt .-%, particularly preferably 8 to 17 wt .-% La ₂ O ₃ included.

Furthermore, the base material preferably contains 1 to 20 wt .-% Al ₂ O ₃ , preferably 5 to 15 wt .-% Al ₂ O ₃ and 1 to 20 wt .-% R ₂ O (alkali oxides), which is preferably to 1 to 20 wt .-% K ₂ O, preferably 5 to 15 wt .-% K ₂ O can act.

According to a further embodiment of the invention, the base material is provided with a doping of Cr ₂ O ₃ , preferably with 0.01 to 5 wt .-%, particularly preferably with 0.02 to 2 wt .-% Cr ₂ O ₃ .

According to a further embodiment of the invention, the base material is provided with a doping which contains Ce ₂ O ₃ , Eu ₂ O ₃ , Tb ₂ O ₃ or Tm ₂ O ₃ .

If the base material is a fluorine-phosphate glass, it preferably contains from 5 to 40% by weight of P ₂ O ₅ and a fluoride content of from 60 to 95% by weight.

Such a base material is preferably doped with 0.01 to 5 wt .-%, preferably with 0.05 to 2 wt .-% of Er ₂ O ₃ and / or Eu ₂ O ₃ .

For example, the base material here with 0.05 to 0.3 wt .-% Er ₂ O ₃ and 0.5 to 2 wt .-% Eu ₂ O ₃ , preferably with about 0.1 wt .-% Er ₂ O ₃ and about 1 wt% Eu ₂ O ₃ .

Further can as a base material according to the invention optical Fluorine crown glasses, in particular FK-52 or FK51 (trade name of Schott), or a lanthanum glass, in particular LAK-8 (trade name of Schott).

Here, the base material may be, for example, an optical glass containing 0.5 to 2 wt% La ₂ O ₃ , 10 to 20 wt% B ₂ O ₃ , 5 to 25 wt% SiO ₂ , 10 to 30 % By weight of SrO, 2 to 10% by weight of CaO, 10 to 20% by weight of BaO, 0.5 to 3% by weight of Li ₂ O, 1 to 5% by weight of MgO, 20 to 50% by weight % By weight of F and refining agent in conventional amounts.

If the base material is formed as Lanthanglas, it may, for example, 30 to 60 wt .-% La ₂ O ₃ , 30 to 50 wt .-% B ₂ O ₃ , 1 to 5 wt .-% SiO ₂ , 1 to 15 wt. -% ZnO, 2 to 10 wt .-% CaO and refining agent in conventional amounts.

such Fluoro-crown glasses or Lanthangläser are preferred with 3 to 100 ppm of non-ferrous metals, preferably doped with cobalt, chromium and / or manganese.

Furthermore, as a base material, a glass ceramic, in particular a lithium-aluminosilicate glass-ceramic is used, such as transparent glass ceramics Robax ^® (Schott-internal designation 87213) or Cleartrans ^® (Schott-internal designation 87233). For this purpose, preferably a doping is used which contains Eu ₂ O ₃ , Er ₂ O ₃ and / or Sm ₂ O ₃ .

Particularly preferably, the doping here contains 0.1 to 5 wt .-% Eu ₂ O ₃ , 0.01 to 0.5 wt .-% Er ₂ O ₃ and / or 0.1 to 2 wt .-% Sm ₂ O. ₃ .

The Base material is in a preferred embodiment of the invention Raw materials produced at the most 100 ppm of rare earths included.

Further For example, the base material preferably has a water content of less as 0.1% by weight, preferably less than 0.01% by weight.

Thereby can Quenching and extinguishing effects be excluded.

Of the Inventive standard can according to a further embodiment of the invention designed as a self-supporting body be, in particular in the cuvette format (preferably 12 × 12 × 50 mm or smaller), in microtiter plate format and slide format (preferably 75 x 25 x 1 mm or smaller), or be made as a capillary.

In addition, it is in principle possible for special applications also an inventive Standard with a substrate made of a substantially non-fluorescent or luminescent material on which the base material is applied with the doping.

in this connection can the base material with the doping as a continuous coating be recorded on the substrate.

On the other hand it is also possible the base material with the doping as a structured coating to apply to the substrate.

such Standards with a substrate of a non-fluorescent or luminescent material, with a coating of an optical transparent base material of glass or glass ceramic, the one Doping with at least one Be constituent, the fluorescent or is luminescent, can be prepared be evaporated by the base material with the doping and is deposited on the substrate.

in this connection the base material can be used with the doping as a target, which evaporates locally by means of an electron beam and on the Substrate is deposited.

is it wanted To achieve a structured coating, so the substrate be masked before deposition, after the coating is at least partially removed, as this in principle from WO-A-03088340 is known.

in this connection can the evaporation and deposition are supported by plasma ions.

The Process for evaporation and deposition of the doped base material on a substrate surface is not on the above mentioned Limited materials, but basically can also be performed at other standards that come from any consist of suitable materials.

It it is understood that the above and the following to be explained Features of the invention not only the combination specified, but also usable in other combinations or in isolation are without departing from the scope of the invention.

Further Features and advantages of the invention will become apparent from the following Description of preferred embodiments with reference to the drawing. Show it:

1 the results of an irradiation test of a glass according to the invention in comparison with a conventional colored glass, wherein the intensity is plotted over the irradiation time;

2 the emission spectra of a lanthanum phosphate glass according to the invention, which is doped with several rare earths compared to a conventional uranyl glass and conventional T-phernyl butadiene in PMMA, each unirradiated, after 30 minutes of irradiation with UV and after 60 minutes of irradiation with UV, the intensity being plotted in arbitrary units over the wavelength in nanometers;

3 the result of measurements to demonstrate good homogeneity and anisotropy on a fluorophosphate glass doped with 1% erbium oxide according to the invention, wherein the intensity is plotted against the wavelength;

4 one 3 corresponding diagram of a fluorine-phosphate glass, which is doped with 1 wt .-% Eu ₂ O ₃ , in turn, the intensity is plotted against the wavelength;

5 a 3 corresponding representation to demonstrate the good anisotropy and homogeneity properties on a lanthanum-phosphate glass doped with Eu ₂ O ₃ ;

6 the results of measurements for testing the anisotropy on the glass according to 5 ;

7 the decay times of FK-5 doped with 10 ppm V ₂ O ₅ and of FP doped with 5 wt% Er ₂ O ₃ , the intensity being plotted in true units over the cooldown in seconds;

8th the cooldowns of the Lathan Phosphate Glass Sample C, with intensity in true unity is plotted in seconds over the cooldown;

9 the maximum intensity of the emission at 510 nm for FK-5 as a function of the doping with V ₂ O ₅ in the range of 10 to 100 ppm, for two series of measurements independently carried out;

10 the long-term behavior of the lathed phosphate glass (sample B) for the emission intensity at 542 nm;

11 the result of homogeneity tests for the maximum intensity at 550 nm for a total of 18 samples with different sampling points from the same glass block of the lanthanum phosphate glass A;

12 the result of homogeneity tests for the maximum intensity at 613 nm for a total of 18 samples with different sampling points from the same glass block of the lanthanum phosphate glass A;

13 the variation of the cooldowns at 550 nm for samples from different sampling points from the same glass block of the lanthanum phosphate glass A and

14 the variation of the decay times at 613 nm for samples from different sampling points from the same glass block of the lanthanum phosphate glass A.

example 1

The compositions of various lanthanum-phosphate glasses, which are individually doped with Cr ₂ O ₃ or multiply doped with rare earth ions, are summarized in Table 1.

Tab. 1

Tab. 1

Example 2

Fluorophosphate glasses (FP glasses) are used which have a P ₂ O ₅ content of 5 to 40% by weight and a fluoride content of 60 to 96% by weight. Single dopants of about 0.1 wt% Er ₂ O ₃ and about 1 wt% Eu ₂ O ₃ are used.

The composition of a FP glass (in% by weight) used as a decay or lifetime standard is:
35% AlF ₃
20% CaF ₂
15% SrF ₂
10% MgF ₂
10% Sr (PO ₃ ) ₂

This glass was doped with 5 wt% Er ₂ O ₃ .

Example 3

optical Fluoro-crown glasses FK-52, FK-53 and Lanthanglas LAK-8 are doped with non-ferrous metals, in the range between 3 and 100 ppm with cobalt, chromium and / or Manganese.

It results in a broadband emission (420 <λ <850 nm) in the for the Bioanalytically relevant excitation range from 400 to 750 nm. The Compositions of the fluoride crown glasses FK51 and FK52 and the Lanthan glands LAK-8 are shown in Table 2.

Tab. 2

Tab. 2

Example 4

It is a lithium-aluminum glass ceramic (LAS glass ceramic) doped with rare earths. To this end, in particular those of Schott Ceran ^® under the brand marketed LAS glass ceramic can be used.

In this case, for example, about 0.1 to 5 wt .-% Eu ₂ O ₃ , 0.01 to 0.5 wt .-% Er ₂ O ₃ and / or 0.1 to 2 wt .-% Sm ₂ O ₃ added become.

The results of various studies for the detection of photostability, homogeneity and anisotropy in various glasses according to the invention are described below with reference to FIGS 1 to 6 explained in more detail.

1 shows the detection of the photo-stability on the glass C according to Table 1 in comparison to the conventional colored glass OG2 (52 wt .-% SiO ₂ , 22.5 wt .-% K ₂ O, 3.9 wt .-% B ₂ O. ₃ , 19.5 wt% ZnO, 1.2 wt% CdS, 0.63 wt% Na ₂ SeO _3, and 0.1 wt% Cd).

It was irradiated with a xenon lamp in the spectral regions 450 to 490 or 510 to 555 nm.

While that Lanthanum phosphate glass according to the invention with SEE doping even after 4 minutes irradiation a drop in intensity of less than 5%, the conventional colored glass OG2 already shows after a short time a strong drop in intensity.

2 shows the results of irradiation with a HOK-4 10W lamp emitting at 365 nm followed by excitation at 365 nm. For comparison, the multiply-doped SEE lanthanum phosphate glass C (Table 1) and a uranium glass GG17 and a T-phernyl butadiene in PMMA. The measured intensity is shown in arbitrary units over the wavelength.

Out The illustration shows that the polymeric fluorescent Material with T-Phernylbutadiene in PMMA a significant drop in the intensity after irradiation shows (see maximum at about 425 nm). Also the uranyl glass GG17, which has its maximum at about 540 nm, shows after irradiation a noticeable drop in intensity, So it is not photostable.

Of the Inventive standard (Sample C according to Table 1) shows a number of pronounced intensity maxima at about 415, 435, 480, 550, 580 and about 620 nm. Between the unirradiated Condition and condition after 30 or 60 minutes of irradiation are practical no intensity differences recognizable.

3 shows the result of testing the anisotropy and homogeneity on a fluoro-phosphate glass with a single doping of about 1 wt% Er ³⁺ . The glass composition was as follows (in mol%): 35% AlF ₃ , 15% SrF ₂ , 30% CaF ₂ , 10% MgF ₂ , 20% P ₂ O ₅ .

The Excitation was at 378 nm and measured at 0 ° (reflection) and 90 °. The measurement was corrected for background and spectral. The homogeneity was checked by four measuring points (N = 4). From the representation of the intensity (in arbitrary Units) the wavelength shows up by the error bars that total the anisotropy is very low (0.02732) and the homogeneity is very good. In the presentation are additional the measured wavelength maxima at 522, 540 and 551 nm.

4 shows a corresponding study of homogeneity and anisotropy on a fluorine-phosphate glass doped with 1 wt .-% Eu ³⁺ . The excitation was at 404 nm. It was measured at 0 ° and 90 ° (reflection). The measurement was corrected for background and spectral. The anisotropy was determined to be 0.01407. The homogeneity was tested at four measuring points.

In turn shows a very good anisotropy and homogeneity.

5 shows a corresponding study on a lanthanum phosphate glass according to sample C (see Table 1). The excitation he followed at 365 nm. It was measured at 0 ° and 90 ° (reflection). The measurement was corrected for background and spectral. The anisotropy was determined to be 0.00783. The homogeneity was tested at four measuring points.

Also This shows a very low anisotropy and a very good Homogeneity.

6 finally shows the measurement of the anisotropy on the lanthanum phosphate glass sample C (see Table 1) as a function of the excitation / emission direction. The measurements were as follows: Measurements were taken at 0 ° (normal case) and 90 °. The emission was measured at 0 ° (measuring point 1) or 90 ° (measuring point 3) or below 0 ° (measuring point 2) or 180 ° (measuring point 4). In addition, measurements were taken at different height positions of the sample (measurement points 5 and 7 or 6 and 8). Measurement points 9 and 10 represent the anisotropy measurements for the arrangement 0-180 °, ie in transmission. The anisotropy values then result (in arbitrary units) relative to the classical 0-90 ° arrangement (excitation / emission).

Also this in turn shows a very good isotropy of the investigated material.

The Preparation of the standards of the invention can essentially according to the person skilled in the art known methods are carried out, with particularly pure starting materials be used (less than 100 ppm of rare earths) and the glasses are "dry" melted, such that the water content is preferably less than 0.01% by weight.

The used luminescent or fluorescent constituents (Fluorophores) can the base material when the glass is melted as oxides or fluorides supplied become.

The known production methods begin with the melting of the glass composition (in which case the steps of melting the batch, refining, homogenizing and conditioning are covered). The melting takes place in ceramic crucibles (ports) at temperatures of about 1100 to about 1550 ° C, preferably in the range of about 1200 to 1360 ° C. The blank melting (refining) is preferably carried out at a slightly lower temperature, for example at about 1200 to 1400 ° C. After a standing phase, the Temperature usually lowered to homogenize the melt. The casting is typically between about 950 and 1050 ° C in a geignete form.

So far it is a LAS glass ceramic, so there is a for such Glass ceramics known temperature treatment for nucleation and subsequent Ceramization.

For special high quality standards can melting in platinum or platinum lined Ceramic crucibles are made to ensure a particularly high purity.

Should a volume-doped according to the invention Base material as a coating on a substantially non-fluorescent or luminescent carrier can be deposited, this can be an evaporation and subsequent deposition as it is basically done from WO-A-03087424 and WO-A-03088340.

For this may be an electron beam generator with a beam deflecting device and a glass target used by an electron beam is taken. Vaporized at the point of impact of the electron beam the glass and beats settling on the substrate to be coated. To the glass of the Targets as possible evaporate evenly to let go, the target is rotated and the electron beam is wobbled. additionally the arrangement may still be a plasma source for generating an ion beam include, in operation, towards the side to be coated directed to the substrate by means of plasma ion assisted vapor deposition (PIAD) with the doped glass layer to coat.

So far the preparation of a structured luminescence standard on a Substrate desired is, then the substrate is first by means of a usual Masking method provided with a masking after the Coating is at least partially removed again.

As a further embodiment, the use of doped FK and FP glasses as the decay or lifetime standard in 7 shown. Shown are the glasses FK-5 (FK51 / FK52 according to Tab. 2) with 10 ppm V ₂ O ₅ , as well as FP (Example 2) doped with 5 wt .-% Er ₂ O ₃ .

at Dopings with rare earth ions and non-ferrous metals become cooldowns observed in the range of a few microseconds to milliseconds.

The Cooldowns are determined as follows: On a fluorescence spectrometer Type FLUOLOG 3, an extension (type IBH TSCPC) was made in such a way, that in addition a pulsed LED light source (1.4 ns or 500 μs, Maximum wavelength at 376 and 489 nm) for the suggestion is used. The detection for a fixed emission wavelength takes place via a Double monochromator and detector. The synchronization of pulsed excitation and detection over a controller that at the same time ensures that the at the detector at different times incoming photons according to their Duration (calculated from the time of suggestion) and being represented. The cooldown is the time for which the maximum intensity by half has been reduced.

Out 7 this results in decay times of 4.1 μs (FK-5 doped with V ₂ O ₅ ) and 52 μs (FP doped with Er ₂ O ₃ ).

The described doped glasses are characterized by the fact that the decay times for dopings less than 500 ppm independent of the doping level.

8th shows the corresponding cooldowns for the Lanthanum Phosphate Glass Sample C (see Table 1). The cooldowns are here in the millisecond range.

at Dopings greater than 0.1 % By weight, the cooldown is dependent the doping level and the glass matrix. With knowledge of these dependencies a calibration is possible.

For the use as device standard It is important that their different sensitivities are taken into account become. This can be done by adding different doping grade used. But then it has to be guaranteed be that intensity also scaled linearly with the doping degree.

In 9 the maximum intensity of the emission at 510 nm for FK-5 doped with 10 ppm V ₂ O ₅ can be seen. Shown are the maximum values of the intensity for two independently performed measurement series.

Finally, standards need be long-term stable in terms of their emission intensity, i. the issue may be over change over a period of 2 years by no more than 5-10%.

In 10 the long-term behavior for the lanthanum-phosphate glass sample B (see Table 1) for the emission at 542 nm is shown. It can be seen that over the course of 24 months the fluctuations in intensity are less than 5%.

To demonstrate the homogeneity or invariance of the fluorescence properties with regard to the sample location from the melt, a total of 18 samples in cuvette form (geometry: 10 × 10 × 40 mm ³ ) were taken from a glass block of the lanthanum phosphate glass A and tested. The result for excitation at 550 nm and 613 nm, respectively, is in the 11 or 12 is shown.

11 shows the maximum intensity at 550 nm at 365 nm excitation for the prepared cuvette samples 1 to 18. It can be seen that the maximum intensity varies from sample to sample no more than 2%.

A similar result shows 12 for the emission at 613 nm. Here, the excitation wavelength is 393 nm, that is, the ff transition of the Eu ³⁺ is explicitly excited. The fluctuations are even in the range of less than 1%.

An even more sensitive detection by determining the decay time for the considered emissions at 550 and 613 nm is in the 13 and 14 shown. The measurement takes place in the so-called single-photon-counting-detection (TPCD) method, in which the individual emitted photons are counted and displayed as a function of the time of the pulsed excitation. The measurement of the decay behavior allows the insight into microscopic absorption and emission processes in fluorescence.

13 shows the decay times for the emissions at 550 nm. The excitation was carried out with a pulsed LED of maximum intensity at 376 nm. 14 shows the result of a corresponding examination at 613 nm.

you recognizes in both cases, that the cooldowns for 550 nm between 2.3 and 2.6 ms or for 613 nm between 2.8 and 3.0 ms lie. The relative deviations are less than 5% and are therefore in the range of the measuring accuracy of the used Device.

• (a) eine Abklingzeit, die bis zu einer Dotierung von etwa 500 ppm unabhängig von der Dotierung ist;
• (b) eine Veränderung der maximalen Intensität von höchstens 10 % oder höchstens etwa 5 % über eine Zeitdauer von 2 Jahren;
• (c) eine Intensitätsvariation von Proben, die aus verschiedenen Probenbereichen eines Glas- bzw. Glaskeramikblocks genommen sind, von höchstens 3 %, vorzugsweise höchstens 2 %, insbesondere von etwa 1 %;
• (d) eine Variation der Abklingzeiten von Proben, die aus verschiedenen Probenbereichen eines Glas- bzw. Glaskeramikblocks genommen sind, von höchstens 10 %, vorzugsweise höchstens etwa 5 %.

Thus, the standards according to the invention specify particularly high-quality standards which fulfill at least one or more of the following characteristics:

• (a) a decay time which is independent of doping up to a doping of about 500 ppm;
• (b) a maximum intensity change of at most 10% or at most about 5% over a period of 2 years;
• (c) an intensity variation of samples taken from different sample areas of a glass or glass-ceramic block of at most 3%, preferably at most 2%, in particular about 1%;
• (d) a variation in the decay times of samples taken from different sample areas of a glass or glass-ceramic block of at most 10%, preferably at most about 5%.

Claims (31)

Standard for the referencing of luminescence signals, with an optically transparent base material of a lanthanum-phosphate glass, a fluorine-phosphate glass, a fluorine crown glass, a lanthanum glass, a from this formed glass ceramic or from a lithium aluminosilicate glass-ceramic, wherein the base material is a bulk doping with at least one rare earth element and / or a non-ferrous metal, in particular cobalt, chromium or manganese contains which is fluorescent or luminescent. Standard according to claim 1, wherein the base material is a lanthanum-phosphate glass containing from 30 to 90% by weight of P ₂ O ₅ , preferably from 50 to 80% by weight, more preferably from 60 to 75% by weight of P ₂ O ₅ , and contains refining agent in conventional amounts. Standard according to Claim 1 or 2, in which the base material is a lanthanum-phosphate glass containing 1 to 30% by weight of La ₂ O ₃ , preferably 5 to 20% by weight, particularly preferably 8 to 17% by weight. Contains La ₂ O ₃ . Standard according to Claim 2 or 3, in which the base material contains 1 to 20% by weight Al ₂ O ₃ , preferably 5 to 15 wt .-% Al ₂ O ₃ . A standard according to any one of claims 2 to 4, wherein the base material contains 1 to 20% by weight of R ₂ O, wherein R is at least one member selected from the group of alkali metals. Standard according to Claim 5, in which the base material contains 1 to 20% by weight of K ₂ O, preferably 5 to 15% by weight of K ₂ O. Standard according to one of the preceding claims, in which the base material is provided with a doping of Cr ₂ O ₃ , preferably with 0.01 to 5 wt .-%, particularly preferably with 0.02 to 2 wt .-% Cr ₂ O ₃ , Standard according to one of the preceding claims, in which the base material is provided with a doping which contains Ce ₂ O ₃ , Eu ₂ O ₃ , Tb ₂ O ₃ or Tm ₂ O ₃ . A standard according to claim 1, 7 or 8, wherein the base material is a fluoro-phosphate glass having 5 to 40% by weight of P ₂ O ₅ and a fluoride content of 60 to 95% by weight. Standard according to one of the preceding claims, in which the base material is doped with 0.01 to 5 wt .-%, preferably with 0.05 to 2 wt .-% of Er ₂ O ₃ and / or Eu ₂ O ₃ . Standard according to claim 10, in which the base material contains from 0.05 to 0.3% by weight Er ₂ O ₃ and from 0.5 to 2% by weight Eu ₂ O ₃ , preferably from about 0.1% by weight It is ₂ O ₃ and about 1 wt .-% Eu ₂ O ₃ doped. Standard according to one of claims 1, 7, 8, 10 or 11, at the base material is a fluorine optical crown glass, in particular FK-52 or FK51, or a lanthanum glass, especially LAK-8. The standard of claim 12, wherein the base material is an optical glass, 0.5 to 2 wt% La ₂ O ₃ , 10 to 20 wt% B ₂ O ₃ , 5 to 25 wt% SiO ₂ , 10 to 30 wt .-% SrO, 2 to 10 wt .-% CaO, 10 to 20 wt .-% BaO, 0.5 to 3 wt .-% Li ₂ O, 1 to 5 wt .-% MgO and 20 contains up to 50% by weight of F and refining agent in conventional amounts. The standard of claim 12, wherein the base material is an optical glass comprising 30 to 60 wt% La ₂ O ₃ , 30 to 50 wt% B ₂ O ₃ , 1 to 5 wt% SiO ₂ , 1 to 15 wt .-% ZnO, 2 to 10 wt .-% CaO and refining agent in conventional amounts. Standard according to claim 12, 13 or 14, wherein the Doping 3 to 100 ppm of non-ferrous metals, preferably of cobalt, Has chromium and / or manganese. Standard according to claim 1, in which there is the base material of a glass ceramic, in particular a lithium aluminosilicate glass-ceramics such as Robax ^® or Cleartrans ^® and having a doping which Eu ₂ O _3, Er ₂ O ₃ and / or Sm ₂ O ₃ , Standard according to Claim 16, in which the doping comprises 0.1 to 5% by weight of Eu ₂ O ₃ , 0.01 to 0.5% by weight of Er ₂ O ₃ and / or 0.1 to 2% by weight. Contains Sm ₂ O ₃ . Standard according to one of the preceding claims, in the base material is made from raw materials which are at most 100 ppm of rare earths included. Standard according to one of the preceding claims, in the base material has a water content of less than 0.1% by weight, preferably less than 0.01% by weight. Standard according to one of the preceding claims, which as a self-supporting body is trained. Standard according to one of claims 1 to 19, comprising a substrate from a substantially non-fluorescent or luminescent Material on which the base material with the doping is applied. Standard according to claim 21, wherein the base material with the doping as a continuous coating on the substrate is included. Standard according to claim 21, wherein the base material with the doping as a structured coating on the substrate is included. Process for the preparation of a standard, in particular according to one of the claims 1 to 23, with a substrate of a substantially non-fluorescent or luminescent material, with a coating of one optically transparent base material made of glass or glass ceramic, the a doping with at least one constituent which is fluorescent or luminescent, in which the base material with the doping is evaporated and deposited on the substrate. The method of claim 24, wherein the base material is used with the doping as a target, by means of an electron beam locally vaporized and deposited on the substrate. The method of claim 24, wherein the substrate before the deposition is provided with a masking after the coating is at least partially removed again. A method according to any one of claims 24 to 26, which comprises plasma ion assisted vapor deposition includes. Use of a standard according to one of claims 1 to 23 as a luminescence standard for the characterization of the long-term stability of luminescence measuring systems. Use of a standard according to one of claims 1 to 23 as the wavelength standard, as luminescence intensity and luminescence lifetime standard for the UV to NIR spectral range or as standard for a standardization of luminescence measurement data of various optical Equipment. Use of a standard according to one of claims 1 to 23 as standard for the characterization and calibration of luminescence measuring systems with time-resolved Luminescence detection in the UV to NIR spectral range. Use of a standard according to one of claims 1 to 23 as standard for the characterization of the intrinsic luminescence of materials in the UV to NIR spectral range of 250-1700 nm.